锂离子电池高温储存后安全性能

:李　佳(1982-),男,河北人,中国科学院上海微系统与信息技术研究所博士生,研究方向:锂离子电池及相关领域,本文联系人;何亮明(1984-),男,江西人,中国科学院上海微系统与信息技术研究所博士生,研究方向:信息处理;杜　(1975-),男,江苏人,中国科学院上海微系统与信息技术研究所副研究员,研究方向:电源管理。李　佳1,何亮明1,2,杜　1,2(1.中国科学院上海微系统与信息技术研究所,上海　200050;2.中国科学院嘉兴无线传感网工程中心,浙江嘉兴　300381):将以LiCoO2、LiNi1/3Co1/3Mn1/3O2和LiFePO4为正极活性物质,人造石墨为负极活性物质的锂离子电池以满电态在高温(55±2℃)下储存30d;通过过充电和加速量热(ARC)实验,比较了高温储存前后的安全性能。高温储存后,正极为LiCoO2和LiNi1/3Co1/3Mn1/3O2的电池在过充电时发生热失控,自加热起始温度分别由130℃和160℃提前到123℃和150℃,说明安全性能降低;正极为LiFePO4的电池耐过充时间延长400s,自加热速率下降,表明安全性能没有降低。:高温储存;　过充电;　加速量热法;　安全性能:TM912.9　　:A　　:1001-1579(2010)03-0158-03SafetyperformanceofLi-ionbatteryafterhightemperaturestorageLIJia1,HELiang-ming1,2,DUChong1,2(1.ShanghaiInstituteofMicrosystemandInformationTechnology,ChineseAcademyofSciences,Shanghai200050,China;2.JiaxingEngineeringCentreforWirelessSensorNetworks,ChineseAcademyofSciences,Jiaxing,Zhejiang300381,China)Abstract:Li-ionbatterieswithLiCoO2,LiNi1/3Co1/3Mn1/3O2andLiFePO4ascathodeactivematerialsandartificialgraphiteasanodeactivematerialwerestoredunderhightemperature(55±2℃)infullchargestatefor30d.Thesafetyperformancebeforeandafterhightemperaturestoragewascomparedbyoverchargeandacceleratingratecalorimeter(ARC)experiments.Afterhightemperaturestorage,thebatterieswithLiCoO2orLiNi1/3Co1/3Mn1/3O2ascathodeexperiencedthermalrunawayduringover-charge,theironsettemperaturesofselfheatedreactionreducedfrom130℃and160℃to123℃and150℃,respectively,indicatedthedegradationofthesafetyperformance.ThesafetyperformanceofbatterywithLiFePO4ascathodehadnodegradation,itsoverchargetimeprolonged400sandselfheatedratereduced.Keywords:hightemperaturestorage;　overcharge;　acceleratingratecalorimeter;　safetyperformance　　[1-2],。(EV)、(HEV)(PHEV),,[3],。,LiCoO2、LiNi1/3Co1/3Mn1/3O2LiFePO4,。1　1.1　LiCoO2(,≥99.5%)、LiNi1/3Co1/3Mn1/3O2(,≥99.5%)LiFePO4(,≥99.5%);(,≥99.5%);1mol/LLiPF6/EC+DMC+DEC(1∶1∶1,,)。、(,≥99.5%)40　32010　　6　　　BATTERY　BIMONTHLYVol.40,No.3Jun.,2010(,)91∶4∶5N-(,),20μm(,),80℃(-0.1MPa,)12h,150MPa120μm,55mm×700mm。,LiCoO2、LiNi1/3Co1/3Mn1/3O2LiFePO49.5g、8.7g8.2g。、(,≥99.6%)97∶1.5∶1.5,15μm(,),40℃12h,150MPa100μm,57mm×750mm。,4.0g。、,80℃12h,、、(6.0g),18650。、(1200±50mAh),。:0.01C2.75～4.20V(LiCoO2、LiNi1/3Co1/3Mn1/3O2)2.50～3.65V(LiFePO4)3。1.2　35,1.00C4.20V(LiCoO2、LiNi1/3Co1/3Mn1/3O2)3.65V(LiFePO4),0.01C,。(55±2℃)30d。1.3　:BTS-51800(),3.00C5.00V(Li-CoO2、LiNi1/3Co1/3Mn1/3O2)12.00V(LiFePO4),0.01C。,。ARCSYS001(ARC)()。ARC--(HWS)(-)(SHR)。2　2.1　2.1.1　LiCoO2LiCoO21。1　LiCoO2Fig.1　OverchargecurvesofthebatterywithLiCoO2ascathodeactivematerial,,38℃。30d,,100℃(1b)。1b,800s,,,,,,。。2.1.2　LiNi1/3Co1/3Mn1/3O2LiNi1/3Co1/3Mn1/3O22。2　LiNi1/3Co1/3Mn1/3O2Fig.2　OverchargecurvesofthebatterywithLiNi1/3Co1/3Mn1/3O2ascathodeactivematerialLiCoO2,,。30d,,100℃(2b)。2b,800s,,,,,。LiCoO2LiNi1/3Co1/3Mn1/3O2,,。,。LiCoO2,。LiCoO2A、B、CD4,1b。A,,5V,,,;BC,,,;D,180℃,,。4:A,,,,。B,,,,。,,,,。C,,,;,SEI,SEI,。,(Li1-xCoO2、Li1-xNi1/3Co1/3Mn1/3O2),。159　3　李　佳,等:锂离子电池高温储存后的安全性能D,,,。2.1.3　LiFePO4LiFePO43。3　LiFePO4Fig.3　OverchargecurvesofthebatterywithLiFePO4ascathodeactivematerialLiFePO4O,,12VLiCoO2,CD,。3,,,84℃,。LiFePO4FePO4,LiFePO4FePO43[4],,,12V,,,。LiFePO430d,400s,。LiCoO2LiNi1/3Co1/3Mn1/3O2,。,,LiFePO4。2.2　ARCARCSHR。LiCoO2、LiNi1/3Co1/3Mn1/3O2LiFePO4SHR4。4　3SHRFig.4　Thechangeofself-heat-rate(SHR)withtemperatureofthe3kindsofbattery4,LiCoO2,130℃,,SHR,15℃/min,130℃,,。,SHR。ARC,(,),,,,,,“”,,,。LiNi1/3Co1/3Mn1/3O2,160℃,LiCoO2,SHR,0.62℃/min,。LiFePO4,SHR,,0.6℃/min。4,LiCoO2LiNi1/3Co1/3Mn1/3O2,130℃160℃123℃150℃,SHR,,。LiCoO2LiNi1/3Co1/3Mn1/3O2;LiFePO4SHR。LiFePO4,。,。3　(55±2℃)。LiCoO2,,LiNi1/3Co1/3Mn1/3O2,,,,SHR。LiFePO4,,。:[1]　RamasamyRP,LeeJW,PopovBN.Simulationofcapacitylossincarbonelectrodeforlithium-ioncellsduringstorage[J].JPowerSources,2007,166(1):266-272.[2]　AurbachD,MarkovskyB,SalitraG,etal.Reviewonelectrode-electrolytesolutioninteractions,relatedtocathodematerialsforLi-ionbatteries[J].JPowerSources,2007,165(2):491-499.[3]　MIAODong-mei(),CHENGXin-qun(),SUNChang-liang(),etal.[J].BatteryBimonthly(),2009,39(2):77-79.[4]　ImachiN,TakanoY,FujimotoH,etal.Layeredcathodeforim-provingsafetyofLi-ionbatteries[J].JElectrochemSoc,2007,154(5):A412-A416.:2009-12-21160　　　　BATTERY　BIMONTHLY　40